CN103333322B - A kind of spirocyclic compound is at the application method of epoxy-resin systems - Google Patents
A kind of spirocyclic compound is at the application method of epoxy-resin systems Download PDFInfo
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- CN103333322B CN103333322B CN201310198179.1A CN201310198179A CN103333322B CN 103333322 B CN103333322 B CN 103333322B CN 201310198179 A CN201310198179 A CN 201310198179A CN 103333322 B CN103333322 B CN 103333322B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims description 9
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000007711 solidification Methods 0.000 claims abstract description 28
- 230000008023 solidification Effects 0.000 claims abstract description 28
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 claims abstract description 12
- 238000007493 shaping process Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 abstract description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000001294 propane Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003413 spiro compounds Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- NPYIRRFPSKFQCL-UHFFFAOYSA-N 3,3-diacetyloxypentanedioic acid Chemical compound C(=O)(O)CC(CC(=O)O)(OC(C)=O)OC(C)=O NPYIRRFPSKFQCL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RVINNYIVIAMDDA-UHFFFAOYSA-N dibutyl benzene-1,2-dicarboxylate;propan-2-one Chemical compound CC(C)=O.CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC RVINNYIVIAMDDA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention discloses a kind of New-type spiro compound-volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane) at the application method of epoxy-resin systems, it comprises the steps: (1) according to 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane consumption is 20 ~ 40% of epoxy resin quality, both is mixed, and shaping after, be heated to 120 ~ 200 DEG C solidification 4 ~ 8h; (2) after fixing: prior to 150 ~ 170 DEG C of solidification 2 ~ 4h; Then in 180 ~ 200 DEG C of solidification 2 ~ 4h; Then in 210 ~ 230 DEG C of solidification 2 ~ 4h, epoxy resin volumetric shrinkage is in the curing process reduced to 0 ~ 0.5%.
Description
Technical field
The present invention relates to the application method of a kind of New-type spiro compound-volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane) at epoxy-resin systems.
Background technology
Can be there is volumetric shrinkage (volumetric shrinkage 2 ~ 5%) in thermosetting epoxy resin, this is fatal defect for epoxy resin and matrix material thereof in the curing process.It can cause the strength of materials to decline, and even causes material to produce the defect such as to come unstuck of the unstable or adhesively bonded joint of tiny crack or cracking, size.In actual applications, the unrelieved stress as the epoxy resin encapsulated material of stress sensitive electronic devices and components can make the performance of electronic devices and components become bad, parameter drift.Unrelieved stress also can make adhesively bonded joint or resin, fiber interface easily by the attack of the environmental factors such as oxygen, water, thus greatly reduces the work-ing life of material.Therefore, the research reducing thermosetting resin cured shrinking percentage is the focus of this area research always.
For solving volumetric shrinkage problem during epoxy resin cure, many scholars have carried out unremitting effort, but generally can only reduce and can not eliminate volumetric shrinkage completely.Theoretically, Expanding Monomer is the most effectual way fundamentally solving epoxy-resin systems volumetric shrinkage problem.But the Expanding Monomer up to now, found also is confined to have bicyclo orthoester (BicyclicOrthoEster), spiro orthoester (SpiroOrthoEster) and spiro orthocarbonate (SpiroOrthoCarbonate) isostructural compound.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of New-type spiro compound-volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane) at the application method of epoxy-resin systems, to reduce epoxy resin and matrix material volumetric shrinkage in the curing process thereof, epoxy-resin systems volumetric shrinkage is reduced to 0 ~ 0.5%.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of spirocyclic compound 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecane, its molecular formula is C
9h
8o
6, structural formula is
Above-mentioned New-type spiro compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane is at the application method of epoxy-resin systems, and its step is as follows:
(1) be 20 ~ 40% of epoxy resin quality according to 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane consumption, both mixed, and shaping after, be heated to 120 ~ 200 DEG C of solidification 4 ~ 8h;
(2) after fixing: prior to 150 ~ 170 DEG C of solidification 2 ~ 4h; Then in 180 ~ 200 DEG C of solidification 2 ~ 4h; Then in 210 ~ 230 DEG C of solidification 2 ~ 4h, epoxy resin volumetric shrinkage is in the curing process reduced to 0 ~ 0.5%.
By such scheme, described in be shaped in casting, injection molding, Wrapping formed, hand pasting forming, pultrusion any one.
By such scheme, described epoxy resin comprises the epoxy resin such as E44, E51, E54, E20, E12.
Above-mentioned New-type spiro compound 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecane is at the another kind of application method of epoxy-resin systems, and its step is as follows:
(1) according to the consumption of DMP-30 promotor is epoxy resin quality 1 ~ 3%, 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecanoic consumption is that 30 ~ 50% of content of epoxy resin is got the raw materials ready, by solidifying agent 2, and 4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] after undecane and organic solvent dissolution used for epoxy resin, add promotor, filler mixes, after shaping, self-vulcanizing 6 ~ 12h;
2) after fixing: prior to 150 ~ 170 DEG C of solidification 2 ~ 4h; Then in 180 ~ 200 DEG C of solidification 2 ~ 4h; Then in 210 ~ 230 DEG C of solidification 2 ~ 4h, epoxy resin volumetric shrinkage is in the curing process reduced to 0 ~ 0.5%.
By such scheme, described in be shaped in casting, injection molding, Wrapping formed, hand pasting forming, pultrusion any one.
By such scheme, described organic solvent is one or any several in acetone, dehydrated alcohol, dibutyl phthalate, toluene.
By such scheme, described promotor is DMP-30.
By such scheme, the consumption of described organic solvent is depending on practical situation, and the consumption of organic solvent of the present invention is 50% of epoxy resin quality.
By such scheme, described filler is aluminium hydroxide, light calcium carbonate etc., and concrete consumption is depending on practical situation, and the consumption of filler of the present invention is 5% of epoxy resin quality.
By such scheme, described epoxy resin comprises the epoxy resin such as E44, E51, E54, E20, E12, CYD128.
The volution tetracarboxylic acid dianhydride (2 that the present invention prepares, 4, 8, 10-tetra-carbonyl-3, 9-dioxa volution [5.5] undecane) to the curing mechanism of epoxy resin as shown in Figure 1: without under the condition of promotor, first volution tetracarboxylic acid dianhydride reacts with the secondary alcohol groups on epoxy main chains, open acid anhydrides, generate half ester, this is ring-opening polymerization, have two singly-bounds and C-O singly-bound fracture after become close to intermolecular model ylid bloom action moment from, usually, this process makes interatomic distance increase 0.146 ~ 0.346nm, thereafter react with epoxide group again and carry out polyaddition reaction, thus make epoxy resin cure, under promotor existent condition, acid anhydrides and tertiary amines promotor generate amphoteric substance, monoesters negatively charged ion is generated afterwards by the methylene radical effect in the nucleation of carboxylic acid negative ion and epoxide group, generate carboxyl negative ion with anhydride reaction afterwards, then react with epoxide group thus make epoxy resin cure.
Compared with prior art, beneficial effect of the present invention is:
The present invention is by a kind of novel epoxy expansion solidifying agent-volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane) application, in order to reduce epoxy resin and matrix material volumetric shrinkage in the curing process thereof, this epoxy-resin systems volumetric shrinkage is reduced to 0 ~ 0.5%, and this kind of expansible solidifying agent can be applied to epoxy resin encapsulated, bonding; The mold pressing, pultrude process etc. of glass fiber reinforced epoxy resin matrix material, its using value and economic worth are given prominence to.
Accompanying drawing explanation
Fig. 1 is the curing mechanism of volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane).
Fig. 2 is the infrared spectrum of volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecane).
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with example, but the present invention is not only confined to the following examples.
New-type spiro compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecanoic preparation method of the present invention comprises the steps:
(1) be 3:2 according to mol ratio, prepare nitrilation agent anhydrous K
4fe (CN)
6for subsequent use with 1,3-bis-bromo-2,2-bis-(brooethyl) propane; Be that 1:1 prepares TBAB according to the mol ratio of phase-transfer catalyst TBAB and 1,3-bis-bromo-2,2-bis-(brooethyl) propane; Without the copper catalyst Cu (OAc) of part
2account for 10% of the total mass of phase-transfer catalyst, be that 5:1 fetches water according to the amount of aqueous solvent and the mol ratio of copper catalyst for subsequent use;
By Cu (OAc)
2catalyzer joins in aqueous solvent, is stirred to homogeneous phase, then adds anhydrous K
4[Fe (CN)
6], TBAB and 1,3-bis-bromo-2,2-bis-(brooethyl) propane, by after container sealing in 180 DEG C of reacting by heating 50min, after reaction terminates, make system naturally cool to room temperature, with extracted with diethyl ether product three times, revolve steaming ether with Rotary Evaporators, GC detects analysis, and make product 1,3-dinitrile-2,2-bis-(nitrile methyl) propane pass through chromatography;
Reaction formula:
(2) under nitrogen atmosphere, in room temperature in the reactor that agitator is housed, 2/3 (total amount of required water and the mol ratio of 1,3-dinitrile-2,2-bis-(nitrile methyl) propane are 1:1.5) of required water cumulative volume is added, topple over 98%H subsequently
2sO
3, sulfuric acid and 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane mol ratio 1:1, , temperature of reaction system is made to be increased to 120 DEG C, then introduce in 1h prepared by above-mentioned steps and obtain 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane, temperature of reaction system controls at 120 DEG C, after being incubated 20min at this temperature subsequently, 1/3 of required water cumulative volume remainder is added in 10min, and temperature is elevated to 130 DEG C of maintenance 6h, reaction terminates rear stopping and stirring, reaction medium layering, make it to naturally cool to 90 DEG C, upper strata and lower layer of water are separated, obtain 1, 3-dicarboxyl-2.2-two (acetoxyl) propane.Through distillation, extraction, recrystallization, productive rate is 91%, and reaction formula is as follows:
(3) according to 1,3-dicarboxyl-2, the mol ratio of 2-bis-(acetoxyl) propane, diacetyl oxide and catalyzer glacial acetic acid is 1:2.1:0.15, by 1,3-dicarboxyl-2,2-bis-(acetoxyl) propane and diacetyl oxide and glacial acetic acid are placed in the there-necked flask with agitator, reflux condensing tube and thermometer, and temperature of reaction controls at 90 DEG C, reaction times is 12h, terminates to reaction solution clarifying reaction; Reaction terminates rear stopping heating, and by product after underpressure distillation, resistates is through trichloromethane recrystallization, and suction filtration drying is weighed, and obtains 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecane, productive rate 96.2%.
Reaction formula is as follows:
Fig. 2 is products therefrom infared spectrum, is analyzed as follows table, therefore confirms that the product obtained according to the method for the invention is 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecane.
Embodiment 1
A kind of New-type spiro compound 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecane is at the application method of epoxy-resin systems, and its step is as follows:
(1) according to the mass fraction, take E51 epoxy resin 100 parts, 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane 33 parts, stirs evenly, then the container filling mixture is placed in ultrasonic cleaner to shake, take out and namely mix, cast, row's bubble, be heated to 150 DEG C of solidification 4h;
(2) after fixing: prior to 170 DEG C of solidification 2h; Then in 190 DEG C of solidification 2h; Then 2h, E51 epoxy resin volumetric shrinkage is in the curing process solidified lower than 0.5% in 210 DEG C.
Adopt the volume change of dilatometer tracking measurement reaction system, measure epoxy resin volumetric shrinkage in the curing process.
Embodiment 2
A kind of New-type spiro compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane is at the application method of epoxy-resin systems, and its step is as follows:
(1) according to the mass fraction, take epoxy resin E44100 part, 2, 4, 8, 10-tetra-carbonyl-3, 9-dioxa volution [5.5] undecane 30 parts, DMP-30 promotor 2 parts is got the raw materials ready, by solidifying agent 2, 4, 8, 10-tetra-carbonyl-3, (volume ratio of acetone and dibutyl phthalate is 1:1 for 9-dioxa volution [5.5] undecane and epoxy resin E44 acetone-dibutyl phthalate mixed solvent, solvent total amount accounts for 50% of epoxy resin quality) dissolve after, add altax P-30 to mix, through glass fiber dipped Wrapping formed after, self-vulcanizing 8h,
2) after fixing: prior to 150 DEG C of solidification 2h; Then in 180 DEG C of solidification 2h; Then in 210 DEG C of solidification 2h, epoxy resin volumetric shrinkage is in the curing process lower than 0.3%.
Embodiment 3
A kind of New-type spiro compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane is at the application method of epoxy-resin systems, and its step is as follows:
(1) according to the mass fraction, take E54 epoxy resin 100 parts, 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane 40 parts, DMP-30 promotor 3 parts is got the raw materials ready, by solidifying agent 2,4,8,10-tetra-carbonyl-3, after 9-dioxa volution [5.5] undecane and E44 acetone used for epoxy resin (volume ratio of acetone and dibutyl phthalate is 1:1, and solvent total amount accounts for 50% of epoxy resin quality) dissolve, add altax P-30 and mix, after row's bubble, glass fiber reinforcement RTM injection molding, self-vulcanizing 6h;
2) after fixing: prior to 170 DEG C of solidification 2h; Then in 190 DEG C of solidification 2h; Then in 220 DEG C of solidification 2h, epoxy resin volumetric shrinkage is in the curing process lower than 0.2%.
Embodiment 4
A kind of New-type spiro compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane is at the application method of epoxy-resin systems, and its step is as follows:
(1) according to the mass fraction, CYD128 epoxy resin 100 parts is taken, 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane 33 parts, filling aluminium hydrate 5 parts, three is mixed, after row's bubble, glass fibre pultrusion, self-vulcanizing 8h;
(2) after fixing: prior to 180 DEG C of solidification 2h; Then in 200 DEG C of solidification 2h; Then 2h, CYD128 epoxy resin volumetric shrinkage is in the curing process solidified lower than 0.4% in 220 DEG C.
Embodiment 5
A kind of New-type spiro compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane is at the application method of epoxy-resin systems, and its step is as follows:
(1) according to the mass fraction, E51 epoxy resin 100 parts is taken, 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane 33 parts, light calcium carbonate filler 5 parts, three is mixed, and sticks with paste technological forming through carbon cloth hand, be heated to 150 DEG C of solidification 4h;
(2) after fixing: prior to 170 DEG C of solidification 2h; Then in 190 DEG C of solidification 2h; Then 2h, E51 epoxy resin volumetric shrinkage is in the curing process solidified lower than 0.5% in 210 DEG C.
Claims (6)
1. spirocyclic compound-2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane is at the application method of epoxy-resin systems, it is characterized in that it comprises the steps:
(1) according to the consumption of DMP-30 promotor is epoxy resin quality 1 ~ 3%, 2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] undecanoic consumption is that 30 ~ 50% of content of epoxy resin is got the raw materials ready, by solidifying agent 2, and 4,8,10-tetra-carbonyl-3,9-dioxa volution [5,5] after undecane and organic solvent dissolution used for epoxy resin, add promotor, filler mixes, after shaping, self-vulcanizing 6 ~ 12h;
2) after fixing: prior to 150 ~ 170 DEG C of solidification 2 ~ 4h; Then in 180 ~ 200 DEG C of solidification 2 ~ 4h; Then in 210 ~ 230 DEG C of solidification 2 ~ 4h, epoxy resin volumetric shrinkage is in the curing process reduced to 0 ~ 0.5%.
2. a kind of spirocyclic compound according to claim 1 is at the application method of epoxy-resin systems, is shaped to any one in casting, injection molding, Wrapping formed, hand pasting forming, pultrusion described in it is characterized in that.
3. a kind of spirocyclic compound according to claim 1 is at the application method of epoxy-resin systems, it is characterized in that described organic solvent is one or any several in acetone, dehydrated alcohol, dibutyl phthalate, toluene.
4. a kind of spirocyclic compound according to claim 1 is at the application method of epoxy-resin systems, it is characterized in that the consumption of described organic solvent is 50% of epoxy resin quality.
5. a kind of spirocyclic compound according to claim 1 is at the application method of epoxy-resin systems, and it is characterized in that described filler is the one in aluminium hydroxide, light calcium carbonate, the consumption of filler is 5% of epoxy resin quality.
6. a kind of spirocyclic compound according to claim 1 is at the application method of epoxy-resin systems, it is characterized in that described epoxy resin is any one in E44, E51, E54, E20, E12 epoxy resin.
Priority Applications (1)
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|---|---|---|---|
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| CN104086750B (en) * | 2014-07-28 | 2017-05-03 | 武汉工程大学 | Application of curing agent 1,2-bi(2,6-dioxo-4-morpholinyl) ethane in epoxy resin system |
| CN110862652B (en) * | 2019-11-29 | 2020-12-08 | 南京航空航天大学 | Low-shrinkage resin cured at room temperature and preparation method thereof |
| CN111732870A (en) * | 2020-07-04 | 2020-10-02 | 上海暄洋化工材料科技有限公司 | Low-shrinkage high-weather-resistance epoxy anticorrosive fireproof coating containing expansion monomer and preparation process thereof |
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